Universität zu Köln

Trillo, Roberto Blanco, Neudoerfl, Joerg M. and Goldfuss, Bernd ORCID: 0000-0002-1814-8818 (2015). An unusually stable chlorophosphite: What makes BIFOP-Cl so robust against hydrolysis? Beilstein J. Org. Chem., 11. S. 313 - 323. FRANKFURT AM MAIN: BEILSTEIN-INSTITUT. ISSN 1860-5397

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Abstract

Two chlorophosphites, the biphenyl-based BIFOP-Cl and the diphenyl ether-based O-BIFOP-Cl, exhibit striking differences regarding their reaction with water. While BIFOP-Cl is nearly completely unreactive, its oxo-derivative O-BIFOP-Cl reacts instantly with water, yielding a tricyclic hydrocarbon unit after rearrangement. The analysis of the crystal structure of O-BIFOP-Cl and BIFOP-Cl revealed that the large steric demand of encapsulating fenchane units renders the phosphorus atom nearly inaccessible by nucleophilic reagents, but only for BIFOP-Cl. In addition to the steric effect, a hypervalent P(III)-O interaction as well as an electronic conjugation effect causes the high reactivity of O-BIFOP-Cl. A DFT study of the hydrolysis in BIFOP-Cl verifies a higher repulsive interaction to water and a decreased leaving tendency of the chloride nucleofuge, which is caused by the fenchane units. This high stability of BIFOP-Cl against nucleophiles supports its application as a chiral ligand, for example, in Pd catalysts.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Trillo, Roberto Blanco UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudoerfl, Joerg M. UNSPECIFIED UNSPECIFIED UNSPECIFIED Goldfuss, Bernd UNSPECIFIED orcid.org/0000-0002-1814-8818 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-405142
DOI:	10.3762/bjoc.11.36
Journal or Publication Title:	Beilstein J. Org. Chem.
Volume:	11
Page Range:	S. 313 - 323
Date:	2015
Publisher:	BEILSTEIN-INSTITUT
Place of Publication:	FRANKFURT AM MAIN
ISSN:	1860-5397
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language GRUNWALD-WINSTEIN EQUATION; NUCLEAR-MAGNETIC-RESONANCE; INTRAMOLECULAR 1,2 SHIFTS; DIALKYLZINC ADDITIONS; N-BUTYLLITHIUM; ASYMMETRIC CATALYSIS; GOVERNS ENANTIOSELECTIVITY; STEREOCHEMICAL INHIBITION; NUCLEOPHILIC-SUBSTITUTION; SIGMA-PARTICIPATION Multiple languages Chemistry, Organic Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/40514